HCID 58671605, compound → HCID 58671591, compound

HRID 1811591Notes

Reaction equation

HRID 1811591 reaction equation
[CH3:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[C:4]([C:11]([S:14]([CH3:17])(=[O:16])=[O:15])([CH3:13])[CH3:12])[N:3]=1>C(O)(=O)C.[Zn]>[CH3:1][C:2]1[C:7]([NH2:8])=[CH:6][CH:5]=[C:4]([C:11]([S:14]([CH3:17])(=[O:16])=[O:15])([CH3:13])[CH3:12])[N:3]=1

Participants

4

Reactant 1

HCID 58671605HCID 58671605, compound

Product 1

HCID 58671591HCID 58671591, compoundYield 59.1%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst2×HCID 176Acetic AcidSolvent

Procedure

To a solution of 2-methyl-6-(2-(methylsulfonyl)propan-2-yl)-3-nitropyridine (1.27 g, 4.92 mmol) in 50 mL acetic acid, zinc dust (1.6 g, 24.5 mmol) was added in small portions under ice-cooling. After 1 h, more zinc dust (ca. 2 g, 31 mmol) was added in small portions and mixture was stirred at room temperature for another hour. Solids were filtered off, washed with CH3CN, and filtrate was concentrated. Residue was purified by CC(CH2Cl2/MeOH 20:1+1% NEt3). Fractions containing product were concentrated and re-purified by HPLC. Fractions containing product were partly concentrated and residue was extracted with 1M NaHCO3 and CH2Cl2. Organic phases were dried over MgSO4, filtered and concentrated to give 2-methyl-6-(2-(methylsulfonyl)propan-2-yl)pyridin-3-amine (0.664 g, 59% yield) as a white solid. 1HNMR (CDCl3, 400 MHz) δ 1.84 (s, 6H), 2.39 (s, 3H), 2.76 (s, 3H), 3.68 (s, 2H), 6.92-6.94 (d, J=8.3 Hz, 1H), 7.29-7.31 (d, J=8.3 Hz, 1H). Exact mass calculated for C10H16N2O2S 228.09 found 229.2 (MH+).

Workup

  1. temperaturecooling
  2. filtrationSolids were filtered off
  3. washwashed with CH3CN, and filtrate
  4. concentrationwas concentrated
  5. customResidue was purified by CC(CH2Cl2/MeOH 20:1+1% NEt3)
  6. additionFractions containing product
  7. concentrationwere concentrated
  8. customre-purified by HPLC
  9. additionFractions containing product
  10. concentrationwere partly concentrated
  11. extractionresidue was extracted with 1M NaHCO3 and CH2Cl2
  12. dry with materialOrganic phases were dried over MgSO4
  13. filtrationfiltered
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-11f05391007141a5a21d9ce03a04e9bf
Source dataset
uspto-grants-2013_01
Patent number
US08362248B2

Reaction notes

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